Preparation of a range of enantioenriched beta-fluoro amines (alpha,beta-disubstituted) is described in which the nitrogen and fluorine atoms are attached to sp(3)-hybridized carbons. The key finding is a chiral bifunctional Bronsted acid/base catalyst that can deliver beta-amino-alpha-fluoro nitroalkanes with high enantio- and diastereoselection. A denitration step renders the nitro group "traceless" and delivers secondary, tertiary, or vinyl alkyl fluorides embedded within a vicinal fluoro amine functional group. A synthesis of each possible stereoisomer of a beta-fluoro lanicemine illustrates the potential ease with which fluorinated small molecules relevant to neuroscience drug development can be prepared in a stereochemically comprehensive manner.